Additives for oil and gas drilling and production

ABSTRACT

A quaternary amine composition selected from the group consisting of Formula I, Formula II, Formula III, and combinations of the same. A method of synthesizing a quaternary amine composition comprising the steps of reacting an alkoxylated dimer diamine with a methyl halogen, where the methyl halogen is selected from the group consisting of methyl chloride, methyl iodine, and combinations of the same; and allowing the reaction to proceed to produce the quaternary amine composition, the quaternary amine composition selected from the group consisting of Formula I, Formula II, Formula III, and combinations of the same. A method of treating a well comprising the steps of introducing an additive-containing well fluid to a well, where the additive-containing well fluid comprises a quaternary amine composition and a well fluid, allowing the additive-containing well fluid to interact with the well, and treating the well with the additive-containing fluid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application a divisional of and claims priority from U.S.Non-Provisional patent application Ser. No. 16/176,584 filed on Oct. 31,2018. For purposes of United States patent practice, this applicationincorporates the contents of the Non-Provisional patent application byreference in its entirety.

TECHNICAL FIELD

Disclosed are compositions for use in oil and gas drilling andproduction. More specifically, embodiments related to compositions foruse as additives in drilling and production fluids are disclosed.

BACKGROUND

Drilling and production fluids tend to be a mixture of multiplecomponents, each enhancing the functionality of the fluids. Inparticular, components can be added to improve the interaction betweenthe fluid and the drilling tools, the interaction between the fluid andthe formation, and the stability of the fluid itself.

There are classes of components that can provide multi-functionality todrilling and production fluids. For example, film forming and cationicmolecules based on amine surfactants, such alkyl pyridines, tallowamines, polyamines, and polyether amines, for example, have long beenused to provide multiple forms of functionality.

Amines and quaternary amine surfactants form film(s) or protectivelayer(s) on casing, drill strings, drilling equipment, and productequipment by chemically or physically adsorbing on the surface of theequipment. The interaction between an amine group and themetal/metal-oxide surface is relatively weak because there is no netpositive charge on it. The interaction strength between the surface andthe quaternary amine surfactant with a net positive charge is mostlyelectrostatic in nature. The charge density on the quaternary aminegroup determines how strongly the molecule is bound to the surface, withgreater binding strength associated with increased corrosion resistance.Stronger adsorption strength improves the film-forming efficiency,including at elevated temperatures when the kinetic energy of themolecules increases making the equipment labile.

SUMMARY

Disclosed are compositions for use in oil and gas drilling andproduction. More specifically, embodiments related to compositions foruse as additives in drilling and production fluids are disclosed.

In a first aspect, a quaternary amine composition is provided. Thequaternary amine composition is selected from the group consisting ofFormula I, Formula II, Formula III, and combinations of the same, whereFormula I is:

where each of R₁ and R₂ is selected from the group consisting of acarbon atom (C—) and a carbon bonded to a hydrogen (—CH), each R₃ isselected from the group consisting of a saturated aliphatic hydrocarbyland an unsaturated aliphatic hydrocarbyl, each R₄ is selected from thegroup consisting of an acyclic hydrocarbyl and an acyclicheterohydrocarbyl, each of R₅ and R₆ is selected from the groupconsisting of a saturated acyclic hydrocarbyl and an unsaturated acyclichydrocarbyl, and X is selected from the group consisting of an iodineion (I—), a chlorine ion (Cl—), and combinations of the same;

where Formula II is:

where each of R₇, R₈, R₉, and R₁₀ is selected from the group consistingof a C— and a —CH, each of R₁₁, R₁₂, R₁₃, and R₁₄ is selected from thegroup consisting of a hydrogen atom (H—), an aliphatic hydrocarbylgroup, and a substituted aliphatic hydrocarbyl group;

where Formula III is:

where R₁₅ is selected from the group consisting of a C—, a —CH, and acarbon bonded to R₂₅ (—CR₂₅), each of R₁₆, R₁₇, R₁₈, and R₁₉ is selectedfrom the group consisting of a C— and a —CH, R₂₀ is selected from thegroup consisting of a C—, a —CH, and a carbon bonded to R₂₆ (—CR₂₆),each of R₂₁, R₂₂, R₂₃, and R₂₄ can include a hydrogen atom (H—), analiphatic hydrocarbyl group, and a substituted aliphatic hydrocarbylgroup, R₂₅ is selected from the group consisting of an aliphatichydrocarbyl group, a substituted aliphatic hydrocarbyl group, andcombinations of the same, R₂₆ is selected from the group consisting ofan aliphatic hydrocarbyl group, a substituted aliphatic hydrocarbylgroup, and combinations of the same.

In certain aspects, R₃ is selected from the group consisting of asaturated C₂-C₂₀ acyclic hydrocarbyl and an unsaturated C₂-C₂₀ acyclichydrocarbyl. In certain aspects, at least one of R₅ and R₆ is anunsaturated C₂-C₂₀ acyclic hydrocarbyl. In certain aspects, both R₅ andR₆ are unsaturated C₂-C₂₀ acyclic hydrocarbyls. In certain aspects, R₃is a saturated C₅-C₁₀ acyclic hydrocarbyl and each of R₅ and R₆ is aC₅-C₁₅ acyclic hydrocarbyl. In certain aspects, where the compositionincludes Formula II, where a ring formed by R₁, R₂, R₇, R₈, R₉, and R₁₀is selected from the group consisting of a cyclohexane, a cyclohexene, acyclohexadiene, and a benzene. In certain aspects, Formula II isselected from the group consisting of Formula IV, Formula V, Formula VI,Formula VII, and Formula VIII, where the compositions of FormulasIV-Formula VIII are:

In certain aspects, the composition includes Formula III, where a doublering formed by R₁, R₂, R₇, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, and R₁₀ isselected from the group consisting of a decahydronapthalene, a tetralin,a dialin, a naphthalene, and other bicyclic compounds.

In certain aspects, Formula III is selected from the group consisting ofFormula IX, Formula X, Formula XI, Formula XII, Formula XIII, FormulaXIV, Formula XV, Formula XVI, Formula XVII, Formula XVIII, Formula XIX,and Formula XX where the compositions of Formulas IX-Formula XX are:

In certain aspects, the substituted aliphatic hydrocarbyl group includesa replacement group, where the replacement group is selected from thegroup consisting of a hydroxyl group, an aminoalkyl group, an alkoxylgroup, an alkylthio group, an amino group, a halo group, a haloalkylgroup, a silyl group, a phosphoryl group, a sulfonyl group, andcombinations of the same.

In certain aspects, the quaternary amine composition includes FormulaXXIII:

where the quaternary amine composition takes the form of Formula I;where R₁ is a carbon bonded to a hydrogen (—CH), R₂ is a carbon atom(C—), each R₃ is a saturated C₆ acyclic hydrocarbyl, R₅ is anunsaturated C₈ acyclic hydrocarbyl, R₆ is an unsaturated C₈ acyclichydrocarbyl, and each R₄ is a saturated C₂ acyclic hydrocarbyl.

In a second aspect, a method of synthesizing a quaternary aminecomposition is provided. The method includes the steps of reacting analkoxylated dimer diamine with a methyl halogen, where the methylhalogen is selected from the group consisting of methyl chloride, methyliodine, and combinations of the same, and allowing the reaction toproceed to produce the quaternary amine composition, the quaternaryamine composition selected from the group consisting of Formula I,Formula II, Formula III, and combinations of the same.

In certain aspects, the step of reacting the alkoxylated dimer diaminewith the methyl halogen is at ambient conditions.

In a third aspect, a method of treating a well is provided. The methodincludes the steps of introducing an additive-containing well fluid to awell, where the additive-containing well fluid includes a quaternaryamine composition, where the additive-containing well fluid includes awell fluid, allowing the additive-containing well fluid to interact withthe well, where the additive-containing well fluid is operable to treatthe well, and treating the well with the additive-containing fluid.

In a third aspect, the quaternary amine composition is selected from thegroup consisting of Formula I, Formula II, Formula III, and combinationsof the same.

In certain aspects, the well fluid is selected from the group consistingof an aqueous-based fluid, an oil-based fluid, and combinations of thesame. In certain aspects, the step of treating a well can be selectedfrom the group consisting of reducing corrosion, stabilizing clays inthe well, stabilizing an emulsion, and combinations of the same.

DETAILED DESCRIPTION

While the scope will be described with several embodiments, it isunderstood that one of ordinary skill in the relevant art willappreciate that many examples, variations and alterations to theapparatus and methods described are within the scope and spirit of theembodiments. Accordingly, the embodiments described here are set forthwithout any loss of generality, and without imposing limitations. Thoseof skill in the art understand that the scope includes all possiblecombinations and uses of particular features described in thespecification. In both the drawings and the detailed description, likenumbers refer to like elements throughout.

The quaternary amine compositions described here can be used asadditives in a drilling and production fluids. The quaternary aminecompositions described here are amine oxide quaternary compounds with agerminal structure, meaning the compounds possess two polar groups andtwo hydrophobic tails. As noted, the charge density on the quaternaryamine group determines how strongly the molecule is bound to thesurface, with greater binding strength associated with increasedcorrosion resistance. Non-germinal quaternary amine surfactants haveweaker adsorption, or binding strength, compared to thegerminal-containing surfactants. Advantageously, the germinal structureof the quaternary amine compositions described here have increasedadsorption strength compared to non-germinal-containing surfactants.Advantageously, quaternary amine compositions have improved film-formingefficiency, including at wellbore temperatures, where the temperaturesare such that the kinetic energy of the molecules increases making theequipment labile as compared to non-germinal-containing surfactants.

As used here, “acyclic” refers to a hydrocarbon or hydrocarbonfunctional group that does not form a ring. Acyclic compounds can besaturated or unsaturated. Acyclic compounds can be straight-chain orbranched-chain. Acyclic can be used to describe acyclic hydrocarbons,acyclic hydrocarbyls, and acyclic heterohydrocarbyls.

As used here, “aliphatic” refers to the class of hydrocarbons orhydrocarbon functional groups that are not aromatics. Aliphatichydrocarbons can by acyclic or cyclic. Aliphatic hydrocarbons can besaturated or unsaturated. An aliphatic hydrocarbyl refers to an acyclicor cyclic, saturated or unsaturated compound composed of carbon andhydrogen that is not aromatic.

As used here, “alkoxylated dimer diamine” refers to a compound havingthe composition of Formula XXI:

where R₁ and R₂ can include a carbon (—C) and a carbon bonded to ahydrogen (—CH); each R₃ can include an aliphatic hydrocarbyl, where eachR₃ can be different or the same; R₄ can include an acyclic hydrocarbyl,an acyclic heterohydrocarbyl, and combinations of the same, where eachR₄ can be the same; each of R₅ and R₆ can include an acyclichydrocarbyl; and X is a halogen that can include iodine ion (I), achlorine ion (Cl), or combinations of the same. Commonly owned U.S.patent application Ser. No. 15/860,831 filed on Jan. 3, 2018, which isincorporated by reference in its entirety, sets forth examples ofalkoxylated dimer diamines that can be used to synthesize the quaternaryamine compositions.

As used here, “aqueous-based fluid” refers to a water-based fluid thatis used to drill a wellbore or for other wellbore activities.Aqueous-based fluids are also known as muds. Aqueous-based fluidssuitable for use in the embodiments can have a salt concentration due tothe presence of salt in the water-based fluid. The salt concentrationcan be in the range from between less than 1 pound per barrel to thesaturation point. Examples of aqueous-based fluids include fresh water,deionized water, sea water, brine, and combinations of the same.

As used here, “clay stabilization” refers to inhibition of clay swellingdue to clay coming in contact with water or water based fluids. Clayswelling can be due to cation exchange with the quaternary amine or byfilm forming.

As used here, “cyclic” refers to a hydrocarbon or hydrocarbon functionalgroup that forms an aromatic or aliphatic hydrocarbon with at least onering or cyclic group in its structural backbone.

As used here, “functional group” or “moiety” or “substituent” refers toan atom or grouping of molecules which can form a bond with othermolecules. A functional group or moiety or substituent maintains itschemical properties or characteristics regardless of what molecule withwhich the functional group is bonded. As used in this application,functional groups are represented by R_(z), where “z” represents aninteger to differentiate the functional groups without implying anythingabout the composition of the functional group.

As used here, “hydrocarbyl” or “hydrocarbyl group” refers to afunctional group composed of carbon and hydrogen. As a functional group,the hydrocarbyl is missing at least one hydrogen, where the hydrocarbylbonds to another chemical group. As used here, a “heterohydrocarbyl”refers to a hydrcarbyl, in which one or more of the carbon atoms issubstituted with a heteroatom. Heteroatoms can include oxygen (O),sulfur (S), nitrogen (N), phosphorous (P), and combinations of the same.

As used here, “saturated” refers to a hydrocarbon functional groupcontaining only carbon-carbon single bonds. In other words, a saturatedaliphatic hydrocarbyl does not contain any carbon-carbon double bonds orcarbon-carbon triple bonds. A saturated acyclic hydrocarbyl group caninclude an alkyl group, the alkyl group is missing one hydrogen wherethe alkyl group bonds to another molecule.

As used here, “substituted” means replaced. In chemistry an atom orfunctional group is substituted when it is replaced with another atom orfunctional group where the molecule contains to remain intact.

As used here, “unsaturated” refers to a hydrocarbon functional groupcontaining at least one carbon-carbon double bond or triple bond. Anunsaturated acyclic hydrocarbyl group can include an alkenyl group or analkynyl group, the alkenyl group or the alkynyl group missing onehydrogen where the alkenyl group or the alkynyl group bonds to anothermolecule.

As used here, “wellbore” refers to a hole drilled into ahydrocarbon-bearing formation, defined by a wellbore wall. The wellborewall can be a face of the formation or can be formed from materialsencasing the face of the formation, where the materials define wellbore.The wellbore can be in fluid communication with the hydrocarbon-bearingformation through the wellbore wall.

The quaternary amine composition can include the composition of FormulaI, the composition of Formula II, the composition of Formula III, orcombinations of the same. The composition of Formula I is:

where R₁ and R₂ can include a carbon atom (C—) and a carbon bonded to ahydrogen (—CH); each R₃ can include an aliphatic hydrocarbyl, where eachR₃ can be different or the same; R₄ can include an acyclic hydrocarbyl,an acyclic heterohydrocarbyl, and combinations of the same, where eachR₄ can be the same; each of R₅ and R₆ can include an acyclichydrocarbyl; and X is a halogen that can include iodine ion (I—), achlorine ion (Cl—), and combinations of the same.

The aliphatic hydrocarbyl of R₃ can include a saturated aliphatichydrocarbyl, an unsaturated aliphatic hydrocarbyl, and combinations ofthe same. The aliphatic hydrocarbyl of R₃ can include an acyclichydrocarbyl, a cyclic hydrocarbyl, and combinations of the same. Thealiphatic hydrocarbyl of R₃ can include a saturated C₂-C₂₀ aliphatichydrocarbyl, alternately an unsaturated C₂-C₂₀ aliphatic hydrocarbyl,alternately a saturated C₂-C₁₂ aliphatic hydrocarbyl, alternately anunsaturated C₂-C₁₂ aliphatic hydrocarbyl, and alternately a saturatedC₅-C₁₀ aliphatic hydrocarbyl. The aliphatic hydrocarbyl of R₃ caninclude a saturated C₂-C₂₀ acyclic hydrocarbyl, alternately anunsaturated C₂-C₂₀ acyclic hydrocarbyl, alternately a saturated C₂-C₁₂acyclic hydrocarbyl, alternately an unsaturated C₂-C₁₂ acyclichydrocarbyl, and alternately a saturated C₅-C₁₀ acyclic hydrocarbyl. Inat least one embodiment, R₃ is a saturated aliphatic hydrocarbyl. In atleast one embodiment, R₃ is a saturated acyclic hydrocarbyl. In at leastone embodiment, R₃ is a saturated C₂-C₉ acyclic hydrocarbyl.

R₄ can be an acyclic hydrocarbyl. The acyclic hydrocarbyl of R₄ caninclude a saturated acyclic hydrocarbyl, an unsaturated acyclichydrocarbyl, and combinations of the same. The acyclic hydrocarbyl caninclude a straight chain hydrocarbyl, a branched chain hydrocarbyl, andcombinations of the same. The saturated acyclic hydrocarbyl has theformula C_(n)H_(2n), where n is an integer in from 2 to 20. Theunsaturated acyclic hydrocarbyl having the formula C_(n)H_(2n-2x), wheren is an integer from 2 to 20 and x is the number of double bonds in theunsaturated acyclic hydrocarbyl.

R₄ can be an acyclic heterohydrocarbyl. The acyclic heterohydrocarbyl ofR₄ can include a saturated acyclic heterohydrocarbyl, an unsaturatedacyclic heterohydrocarbyl, and combinations of the same. The acyclicheterohydrocarbyl can include a straight chain heterohydrocarbyl, abranched chain hydrocarbyl, and combinations of the same. In at leastone embodiment, R₄ can be an acyclic heterohydrocarbyl, where the heteroatom is oxygen (O—) having the formula (C_(n)H_(2n)O)_(x)C_(n)H_(2n),where n is an integer from 2 to 20, alternately an integer from 2 to 5,and alternately from 2 to 4 and x is an integer from 1 to 10,alternately an integer from 1 to 5, alternately an integer from 1 to 4,alternately an integer from 2 to 10, alternately an integer from 2 to 5,and alternately an integer from 4 to 10. In at least one embodiment, R₄can be an acyclic heterohydrocarbyl, where the hetero atom is oxygen(O—) having the formula (C_(n)H_(2n-2)O)_(x)C_(n)H_(2n), where n is aninteger from 2 to 20, alternately an integer from 2 to 5, andalternately from 2 to 4 and x is an integer from 1 to 10, alternately aninteger from 1 to 5, alternately an integer from 1 to 4, alternately aninteger from 2 to 10, alternately an integer from 2 to 5, andalternately an integer from 4 to 10. In at least one embodiment, R₄ canbe an acyclic heterohydrocarbyl, where the hetero atom is oxygen (O—)having the formula (C_(n)H_(2n-2)O)_(x)C_(n)H_(2n-2), where n is aninteger from 2 to 20, alternately an integer from 2 to 5, andalternately from 2 to 4 and x is an integer from 1 to 10, alternately aninteger from 1 to 5, alternately an integer from 1 to 4, alternately aninteger from 2 to 10, alternately an integer from 2 to 5, andalternately an integer from 4 to 10.

The R₅ and R₆ can form the hydrophobic tails of the quaternary aminecomposition. The quaternary amine composition can have two hydrophobictails, alternately three hydrophobic tails, alternately four hydrophobictails, and alternately one less hydrophobic tail than would make thequaternary amine composition insoluble in the fluid. In at least oneembodiment, the quaternary amine composition contains two hydrophobictails. In at least one embodiment, the quaternary amine compositioncontains three hydrophobic tails.

R₅ and R₆ can both be the same compound or class of compounds, or can bedifferent compounds or different classes of compounds. The acyclichydrocarbyl of R₅ and R₆ can be a saturated acyclic hydrocarbyl, anunsaturated acyclic hydrocarbyl, and combinations of the same. Theacyclic hydrocarbyl of R₅ and R₆ can include a saturated C₂-C₂₀ acyclichydrocarbyl, an unsaturated C₂-C₂₀ acyclic hydrocarbyl, a saturatedC₅-C₁₅ acyclic hydrocarbyl, an unsaturated C₅-C₁₅ acyclic hydrocarbyl, asaturated C₆-C₁₂ acyclic hydrocarbyl, an unsaturated C₆-C₁₂ acyclichydrocarbyl, and combinations of the same. In at least one embodiment,both R₅ and R₆ are acyclic hydrocarbyls, but the specific acyclichydrocarbyls are different. In at least one embodiment, R₅ and R₆ arethe same acyclic hydrocarbyls. In at least one embodiment, one of R₅ orR₆ is a saturated C₂-C₂₀ acyclic hydrocarbyl and the other is anunsaturated C₂-C₂₀ acyclic hydrocarbyl.

In at least one embodiment, R₃ is a saturated C₅-C₁₀ acyclic hydrocarbyland each of R₅ and R₆ is a C₅-C₁₅ acyclic hydrocarbyl.

The hydroxyl groups bonded to the R₄ functional groups can behydrophilic.

The composition of Formula II is:

where R₁, R₂, R₃, R₄, R₅, R₆, and X are described with reference toFormula I, each of R₇, R₈, R₉, and R₁₀ can include a carbon atom (C—)and alternately a carbon bonded to a hydrogen (—CH); and each of R₁₁,R₁₂, R₁₃, and R₁₄, can include a hydrogen atom (H—), an aliphatichydrocarbyl group, a substituted aliphatic hydrocarbyl group, an alkylgroup, an aminoalkyl group, an aminoalkoxy group, a hydroxyl group, analkoxyl group, an alkylthio group, an amino group, a halo, a haloalkylgroup, a silyl group, a phosphoryl group, a sulfonyl group, andcombinations of the same.

The ring of Formula II formed by R₁, R₂, R₇, R₈, R₉, and R₁₀, caninclude a saturated cyclic hydrocarbyl and an unsaturated cyclichydrocarbyl. The ring of Formula II can include a cyclohexane, acyclohexene, a cyclohexadiene, and a benzene. The ring of Formula II caninclude the compositions of Formulas IV to VIII:

In the formulas, a wavy line “˜˜˜˜” represents the quaternary aminesection of the quaternary amine composition, shown in Formula IIbeginning with the R₃ functional groups. Formula IV includes acyclohexane, where each of R₁, R₂, R₇, R₈, R₉, and R₁₀ are a carbonbonded to a hydrogen (—CH). Formula V includes a cyclohexene, where eachof R₁ and R₂ is a carbon atom (C—) and each of R₇, R₈, R₉, and R₁₀ is acarbon bonded to a hydrogen (—CH). Formula VI and Formula VII include acyclohexadiene, where each of R₁ and R₂ is a carbon atom (C—) and two ofR₇, R₈, R₉, and R₁₀ are a carbon atom (C—) and the remaining two are acarbon atom bonded to a hydrogen (—CH). Formula VIII includes a benzene,where all of R₁, R₂, R₇, R₈, R₉, and R₁₀ are a carbon atom (C—).

Returning to Formula II with reference to Formulas IV to VIII, each ofthe functional groups R₁₁, R₁₂, R₁₃, and R₁₄, can be a hydrogen atom(H—), an aliphatic hydrocarbyl group, a substituted aliphatichydrocarbyl group, and combinations of the same. The aliphatichydrocarbyl group can include a saturated acyclic hydrocarbyl and anunsaturated acyclic hydrocarbyl. The saturated acyclic hydrocarbyl canbe a saturated C₁-C₁₀₀ acyclic hydrocarbyl, alternately a saturatedC₁-C₅₀ acyclic hydrocarbyl, alternately a saturated C₁-C₂₅ acyclichydrocarbyl, alternately a saturated C₁-C₁₀ acyclic hydrocarbyl,alternately a saturated C₂-C₂₀ acyclic hydrocarbyl, and alternately asaturated C₂-C₁₀ acyclic hydrocarbyl. The unsaturated acyclichydrocarbyl can be an unsaturated C₁-C₁₀₀ acyclic hydrocarbyl,alternately an unsaturated C₁-C₅₀ acyclic hydrocarbyl, alternately anunsaturated C₁-C₂₅ acyclic hydrocarbyl, alternately an unsaturatedC₁-C₁₀ acyclic hydrocarbyl, alternately an unsaturated C₂-C₂₀ acyclichydrocarbyl, and alternately an unsaturated C₂-C₁₀ acyclic hydrocarbyl.

The substituted aliphatic hydrocarbyl group can include a substitutedsaturated aliphatic hydrocarbyl group and a substituted unsaturatedaliphatic hydrocarbyl group. The substituted aliphatic hydrocarbyl groupcan include a replacement group, where the replacement group replacesone or more of the carbons in the substituted aliphatic hydrocarbylgroup. The replacement group can include a hydroxyl group, an aminoalkylgroup, an alkoxyl group, an alkylthio group, an amino group, a halogroup, a haloalkyl group, a silyl group, a phosphoryl group, a sulfonylgroup, and combinations of the same.

The composition of Formula III is:

where R₁, R₂, R₃, R₄, R₅, R₆, and X are described with reference toFormula I; R₇, R₁₀, R₁₁, and R₁₄, are described with reference toFormula II; R₁₅ can include a carbon atom (C—), a carbon atom bonded toa hydrogen (—CH), and a carbon bonded to R₂₅ (—C—R₂₅); R₁₆, R₁₇, R₁₈,R₁₉ can include a carbon atom (C—) and a carbon bonded to a hydrogen(—CH); R₂₀ can include a carbon atom (C—), a carbon atom bonded to ahydrogen (—CH), and a carbon bonded to R₂₆ (—C—R₂₆); each of R₂₁, R₂₂,R₂₃, and R₂₄ can include a hydrogen atom (H—), an aliphatic hydrocarbylgroup, a substituted aliphatic hydrocarbyl group and combinations of thesame; each of R₂₅ and R₂₆ can include an aliphatic hydrocarbyl group, asubstituted aliphatic hydrocarbyl group and combinations of the same.

The double ring of Formula III formed by R₁, R₂, R₇, R₁₅, R₁₆, R₁₇, R₁₈,R₁₉, R₂₀, and R₁₀, can include a saturated cyclic hydrocarbyl, anunsaturated cyclic hydrocarbyl, and combinations of the same. While thedouble ring of Formula III is shown such that the two rings areconnected between the R₁₅ and R₂₀ moieties, one of skill in the art canappreciate that the second ring can be shifted, such that the two ringsare connected between R₇ and R₁₅ such that the ring is formed from R₇,R₁₆, R₁₇, R₁₈, R₁₉, and R₁₅, alternately between R₂₀ and R₁₀ such thatthe ring is formed from R₂₀, R₁₆, R₁₇, R₁₈, R₁₉, and R₁₀. The doublering of Formula III can include a decahydronapthalene, a tetralin, adialin, a naphthalene, and other bicyclic compounds. The ring of FormulaIII can include the compositions of Formulas IX to XX:

In the formulas, a wavy line “˜˜˜˜” represents the quaternary aminesection of the quaternary amine composition, shown in Formula IIIbeginning with the R₃ functional groups. Formula XII and Formula XIIIinclude a tetralin, where each of R₁, R₂, R₇, R₁₅, R₂₀, and R₁₀ is acarbon atom (C—) and each of R₁₆, R₁₇, R₁₈, and R₁₉ are a carbon bondedto a hydrogen (—CH) or where each of R₁, R₂, R₇, and R₁₀ are a carbonbonded to a hydrogen (—CH) and each of R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, and R₂₀is a carbon atom (C—). Formula XIX includes a naphthalene, where each ofR₁, R₂, R₇, R₁₀, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, and R₂₀ is a carbon atom (C—).Formula XX includes a decalin where each of R₁, R₂, R₇, R₁₀, R₁₅, R₁₆,R₁₇, R₁₈, R₁₉, and R₂₀ is a carbon bonded to a hydrogen (—CH).

Returning to Formula III with reference to Formulas IX to XX, each ofthe functional groups R₁₁, R₁₄, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆ can bea hydrogen atom (H—), an aliphatic hydrocarbyl group, a substitutedaliphatic hydrocarbyl group, and combinations of the same. The aliphatichydrocarbyl group can include a saturated acyclic hydrocarbyl and anunsaturated acyclic hydrocarbyl. The saturated acyclic hydrocarbyl canbe a saturated C₁-C₁₀₀ acyclic hydrocarbyl, alternately a saturatedC₁-C₅₀ acyclic hydrocarbyl, alternately a saturated C₁-C₂₅ acyclichydrocarbyl, alternately a saturated C₁-C₁₀ acyclic hydrocarbyl,alternately a saturated C₂-C₂₀ acyclic hydrocarbyl, and alternately asaturated C₂-C₁₀ acyclic hydrocarbyl. The unsaturated acyclichydrocarbyl can be an unsaturated C₁-C₁₀₀ acyclic hydrocarbyl,alternately an unsaturated C₁-C₅₀ acyclic hydrocarbyl, alternately anunsaturated C₁-C₂₅ acyclic hydrocarbyl, alternately an unsaturatedC₁-C₁₀ acyclic hydrocarbyl, alternately an unsaturated C₂-C₂₀ acyclichydrocarbyl, and alternately an unsaturated C₂-C₁₀ acyclic hydrocarbyl.

The substituted aliphatic hydrocarbyl group can include a substitutedsaturated aliphatic hydrocarbyl group and a substituted unsaturatedaliphatic hydrocarbyl group. The substituted aliphatic hydrocarbyl groupcan include a saturated acyclic hydrocarbyl group containing at least 1carbon after substitution, alternately at least 2 carbons aftersubstitution, alternately between 1 carbon and 19 carbons aftersubstitution, and alternately between 1 carbon and 100 carbons aftersubstitution. The substituted aliphatic hydrocarbyl group can include areplacement group, where the replacement group replaces one or more ofthe carbons in the substituted aliphatic hydrocarbyl group. Thereplacement group can include a hydroxyl group, an aminoalkyl group, analkoxyl group, an alkylthio group, an amino group, a halo group, ahaloalkyl group, a silyl group, a phosphoryl group, a sulfonyl group,and combinations of the same.

The functional groups R₁₁, R₁₄, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆ can bethe same moiety, and alternately can be a different moiety. The moietiescan result in the quaternary amine compositions having more than twotails.

The quaternary amine compositions can be synthesized by reacting analkoxylated dimer diamine with a methyl halogen.

The methyl halogen can include methyl chloride, methyl iodine, andcombinations of the same.

The alkoxylated dimer diamine can produce a non-ionic surfactant. Thereaction of the alkoxylated dimer diamine with the methyl halogen canresult in quaternary amines on the molecular backbone.

The reaction between the alkyoxylated dimer diamine and the methylhalogen can occur across a range of temperatures and pressures. In atleast one embodiment, the reaction between the alkyoxylated dimerdiamine and the methyl halogen can occur at ambient conditions.

The quaternary amine compositions produced by the described method cantake the forms of Formula I, Formula II, and Formula III. In at leastone embodiment, the quaternary amine composition can include thecomposition of Formula XXII:

where the quaternary amine composition takes the form of Formula I;where R₁ is a carbon bonded to a hydrogen (—CH), R₂ is a carbon atom(C—), each R₃ is a saturated C₆ acyclic hydrocarbyl, R₅ is anunsaturated C₈ acyclic hydrocarbyl, R₆ is an unsaturated C₈ acyclichydrocarbyl, and R₄ can include an acyclic hydrocarbyl, an acyclicheterohydrocarbyl, and combinations of the same.

In at least one embodiment, the quaternary amine composition can includethe composition of Formula XXIII:

where the quaternary amine composition takes the form of Formula II;where R₁, R₂, R₇, R₈, R₉, and R₁₀ form a cyclohexene ring, where each ofR₁, R₂, R₉, and R₁₀ is a carbon bonded to a hydrogen (—CH), each of R₇and R₈ is a carbon atom (C—), each R₃ is a saturated C₇ acyclichydrocarbyl, R₁₃ is a saturated C₆ acyclic hydrocarbyl, R₁₀ is anunsaturated C₈ acyclic hydrocarbyl, and R₄ can include an acyclichydrocarbyl, an acyclic heterohydrocarbyl, and combinations of the same.

In at least one embodiment, the quaternary amine composition can includethe composition of Formula XXIV:

where the quaternary amine composition takes the form of Formula II;where R₁, R₂, R₇, R₈, R₉, and R₁₀ form a benzene ring, where each of R₁,R₂, R₇, R₈, R₉, and R₁₀ is a carbon atom (C—), each R₃ is a saturated C₇acyclic hydrocarbyl, R₁₃ is a saturated C₆ acyclic hydrocarbyl, R₁₀ is asaturated C₈ acyclic hydrocarbyl, and R₄ can include an acyclichydrocarbyl, an acyclic heterohydrocarbyl, and combinations of the same.

In at least one embodiment, the quaternary amine composition can includethe composition of Formula XXV:

where the quaternary amine composition takes the form of Formula III;where R₁, R₂, R₇, R₁₅, R₂₀, and R₁₀ form a cyclohexene ring, where eachof R₁, R₂, R₁₅, R₂₀, and R₁₀ is a carbon bonded to a hydrogen (—CH) andR₇ is a carbon atom (C—), the second ring is connected between R₇ andR₁₅, and R₇, R₁₆, R₁₇, R₁₈, R₁₉, and R₁₅ forms a cyclohexene ring, whereRib is a carbon atom, each of R₁₇, R₁₈, and R₁₉ are carbon bonded to ahydrogen (—CH), each of R₂₁, and R₂₄ is a hydrogen atom (—H), R₂₂ is asaturated C₆ acyclic hydrocarbyl, R₂₃ is a saturated C₄ acyclichydrocarbyl, and R₄ can include an acyclic hydrocarbyl, an acyclicheterohydrocarbyl, and combinations of the same.

In at least one embodiment, the quaternary amine composition can includethe composition of Formula XXVI:

where the quaternary amine composition takes the form of Formula III;where R₁, R₂, R₇, R₁₅, R₂₀, and R₁₀ form a cyclohexene ring, where eachof R₁ and R₂ is a carbon bonded to a hydrogen (—CH), each of R₇, R₁₅,R₂₀, and R₁₀ is a carbon atom (C—), the second ring is connected betweenR₂₀ and R₁₀, and R₂₀, R₁₆, R₁₇, R₁₈, R₁₉, and R₁₀ forms a cyclohexanering, where each of R₁₆, R₁₇, R₁₈, and R₁₉ are carbon bonded to ahydrogen (—CH), each of R₁₁, R₁₄, R₂₄, R₂₅, and R₂₆ is a hydrogen atom(—H), R₂₁ is a saturated C₇ acyclic hydrocarbyl, R₂₂ is a saturated C₆acyclic hydrocarbyl, R₂₃ is an unsaturated C₈ acyclic hydrocarbyl, R₂₄is a saturated acyclic heterohydrocarbyl having the form C₈N(R₄)₂(OH)₂and R₄ can include an acyclic hydrocarbyl, an acyclic heterohydrocarbyl,and combinations of the same.

The quaternary amine compositions can reduce corrosion, can stabilizeclay compounds, and can stabilize emulsions. Advantageously, thegerminal-containing surfactants of the quaternary amine compositionshave stronger adsorption, or binding strength, as compared tonon-geminal quaternary amine surfactants.

The quaternary amine compositions can be used as additives in wellfluids. The quaternary amine compositions can be added to the wellfluids before introducing the well fluid to the well and alternatelywhile the well fluid is being introduced to the well. The well fluidscan include drilling fluids, fracturing fluids, completion fluids andcombinations of the same. The well fluids can be aqueous-based fluids oroil-based fluids. The quaternary amine compositions can be mixed as anadditive in a well fluid to produce an additive-containing well fluid.The quaternary amine surfactant can be present in theadditive-containing well fluid in the range from 0.5 pounds per barrel(ppb) to 10 ppb. The additive-containing well fluid can be used to treata wellbore. Treating a well can include reducing corrosion, stabilizingclays in the formation, stabilizing an emulsion, and combinations of thesame.

In at least one embodiment, the quaternary amine composition can beadded to an aqueous-based fluid for use as a well fluid to reducecorrosion by the aqueous-based fluid. The additive-containing well fluidcan treat a wellbore, where a least a portion of the quaternary aminecomposition in the additive-containing well fluid is operable to contacta metal material in the wellbore. The metal material can include anytype of metal suitable for use in a wellbore. Upon contact with metalmaterial, the portion of the quaternary amine composition can form afilm on the surface of the metal material. The film formed on thesurface of the metal material can form a barrier to water. The filmformed on the surface of the metal material can reduce corrosion of themetal material by preventing the well fluid from contacting the metalmaterial. The film formed by the quaternary amine compositions canprotect against any corrosive fluids. Examples of corrosive fluidsinclude water, acids, bases, carbon dioxide, hydrogen sulfide, andcombinations of the same.

In at least one embodiment, the quaternary amine composition can beadded to an aqueous-based fluid for use as a well fluid to improve claystabilization. The additive-containing well fluid can treat a wellborewall, where at least a portion of the quaternary amine composition inthe additive-containing well fluid is operable to contact a claymaterial in fluid contact with the wellbore wall. The clay material caninclude any kind of clay material found in a hydrocarbon-bearingformation. The clay material can be in the wellbore wall or in thehydrocarbon-bearing formation. On contact with the clay material, theportion of the quaternary amine composition can form a film on the claymaterial.

In at least one embodiment, the quaternary amine surfactant can be addedto an oil-based fluid for use as a well fluid to stabilize the emulsion.

The quaternary amine compositions described here are positively chargedand act as corrosion inhibitors. In contrast, the reactant alkoxylateddimer diamines can be used as secondary emulsifiers.

EXAMPLES Example 1. Additive as Corrosion Inhibitor

Example 1 tested the quaternary amine composition as a corrosioninhibitor, using the quaternary amine composition of Formula I, havingthe specific form of Formula XXVII:

where the quaternary amine composition takes the form of Formula XXII;where R₁ is a carbon bonded to a hydrogen (—CH), R₂ is a carbon atom(C—), each R₃ is a saturated C₆ acyclic hydrocarbyl, R₅ is anunsaturated C₈ acyclic hydrocarbyl, R₆ is an unsaturated C₈ acyclichydrocarbyl, and each R₄ is a saturated C₂ acyclic hydrocarbyl.

Two 1018 steel coupons were tested, Coupon A and Coupon B. Each couponwas weighed to get an initial mass. Then each steel coupon was rolled ina vessel pressurized under 500 pounds per square inch (psi) carbondioxide (CO₂) at 120 degree Fahrenheit (deg F.) for 16 hours in a twopercent (2%) sodium chloride (NaCl) solution. Coupon A was untreated.Coupon B was treated with a 0.6% or 6 gallons per thousand gallons (gpt)dose rate of the quaternary amine composition of Formula XXVII. Aftertesting, each coupon was cleaned according to API and NACE standards,including weighing each coupon to get a final mass. The results areshown in Table 1.

TABLE 1 Results of Example 1 Initial Final Mass Surface Corrosion CouponMetal Mass (g) Mass (g) Loss (g) Area (in²*) Factor Loss (lb/ft²) A(untreated) 1018 Steel 8.0157 7.27858 0.73712 1.4594 0.22 0.160 B(treated) 1018 Steel 8.0179 7.825 0.1929 1.49433 0.21 0.041 *inches(in²)

The results show that the treatment of Coupon B with the quaternaryamine composition reduced corrosion loss by nearly 400% and maintainedCoupon B at less than the established failure criteria of less than 0.5pounds per square foot (1b/ft²) corrosion loss. While Example 1 providesfor a composition where the quaternary amine composition is added to anaqueous solution, the quaternary amine composition can be added to anoil composition.

Example 2. Additive as Clay Swelling Inhibitor

Example 2 compared different inhibitors for their clay swellinginhibition efficiency. The different inhibitors included the quaternaryamine composition of Formula XXVII (Sample 2) and choline chloride(Sample 3). Choline chloride is an industry standard for inhibiting clayswelling and is considered to be an excellent performer. The twoinhibitors were compared to a sample with no inhibitor (Sample 3). Afluid was prepared according to Table 2 for use in a clay swelling test.The fluid according to the composition of Table 1 was mixed for 5minutes (min) and then allowed to remain static for 15 minutes (min).Then 5 milliliters (mL) were used for the clay swelling test. The clayswelling test was performed using a Fann model 440 Capillary SuctionTimer (CST).

TABLE 2 Fluid Composition for Clay Swelling Test Component Amount inFluid Water 250 grams (g) Bentonite 5.1 g Silica Flour 24.9 g Inhibitor5 mL

The results from the clay swelling test are shown in Table 3.

TABLE 3 Results of Example 2. Time (s) Sample normalized 1 (Noinhibitor) 482.8 2 (Quaternary Salt) 1.7 3 (Choline Chloride) 2.9

The results show that the quaternary amine composition is efficient atinhibiting clay swelling and can be used as a clay control agent. A CSTvalue of less than 50 seconds (s) is considered to have excellentefficiency at inhibiting clay swelling. In general, the lower the value,the better the performance of the inhibitor. Each of the Examplesillustrate that the quaternary amine composition can be used to improveproduction fluids.

Although the technology has been described in detail, it should beunderstood that various changes, substitutions, and alterations can bemade hereupon without departing from the principle and scope.Accordingly, the scope of the embodiments should be determined by thefollowing claims and their appropriate legal equivalents.

The singular forms “a,” “an,” and “the” include plural referents, unlessthe context clearly dictates otherwise.

Optional or optionally means that the subsequently described event orcircumstances can or may not occur. The description includes instanceswhere the event or circumstance occurs and instances where it does notoccur.

Ranges may be expressed as from one particular value to anotherparticular value. When such a range is expressed, it is to be understoodthat another embodiment is from the one particular value to the otherparticular value, along with all combinations within said range.

Throughout this application, where patents or publications arereferenced, the disclosures of these references in their entireties areintended to be incorporated by reference into this application, in orderto more fully describe the state of the art, except when thesereferences contradict the statements made here.

As used here and in the appended claims, the words “comprise,” “has,”and “include” and all grammatical variations thereof are each intendedto have an open, non-limiting meaning that does not exclude additionalelements or steps.

What is claimed is:
 1. A method of synthesizing a quaternary aminecomposition, the method comprising the steps of: reacting an alkoxylateddimer diamine with a methyl halogen to produce the quaternary aminecomposition, where the methyl halogen is selected from the groupconsisting of methyl chloride, methyl iodine, and combinations of thesame, where the quaternary amine composition comprises Formula I, whereFormula I is:

where: each of R₁ and R₂ is selected from the group consisting of acarbon atom (C—) and a carbon bonded to a hydrogen (—CH), each R₃ isselected from the group consisting of a saturated aliphatic hydrocarbyland an unsaturated aliphatic hydrocarbyl, each R₄ is selected from thegroup consisting of an acyclic hydrocarbyl and an acyclicheterohydrocarbyl, each of R₅ and R₆ is selected from the groupconsisting of a saturated acyclic hydrocarbyl and an unsaturated acyclichydrocarbyl, X is selected from the group consisting of an iodine ion(I—), a chlorine ion (Cl—), and combinations of the same.
 2. The methodof claim 1, where the step of reacting the alkoxylated dimer diaminewith the methyl halogen is at ambient conditions.
 3. The method of claim1, where Formula I is:

where the quaternary amine composition takes the form of Formula I;where R₁ is a carbon bonded to a hydrogen (—CH), R₂ is a carbon atom(C—), each R₃ is a saturated C₆ acyclic hydrocarbyl, R₅ is anunsaturated C₈ acyclic hydrocarbyl, R₆ is an unsaturated C₈ acyclichydrocarbyl, and each R₄ is a saturated C₂ acyclic hydrocarbyl.